EP2441532B1 - Nickelplattiertes stahlblech und verfahren zur herstellung eines batteriegehäuses unter verwendung des nickelplattierten stahlblechs - Google Patents

Nickelplattiertes stahlblech und verfahren zur herstellung eines batteriegehäuses unter verwendung des nickelplattierten stahlblechs Download PDF

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EP2441532B1
EP2441532B1 EP10785906.8A EP10785906A EP2441532B1 EP 2441532 B1 EP2441532 B1 EP 2441532B1 EP 10785906 A EP10785906 A EP 10785906A EP 2441532 B1 EP2441532 B1 EP 2441532B1
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Prior art keywords
steel sheet
plated steel
diffusion layer
plating
surface roughness
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English (en)
French (fr)
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EP2441532A1 (de
EP2441532A4 (de
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Shinichi Takematsu
Eiji Okamatsu
Hideyuki Minagi
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/227—Surface roughening or texturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D51/00—Making hollow objects
    • B21D51/16—Making hollow objects characterised by the use of the objects
    • B21D51/26—Making hollow objects characterised by the use of the objects cans or tins; Closing same in a permanent manner
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4998—Combined manufacture including applying or shaping of fluent material
    • Y10T29/49982—Coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12937—Co- or Ni-base component next to Fe-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • the present invention relates to a Ni-plated steel sheet where the occurrence of scratches at the time of forming a battery can is suppressed and a method of manufacturing a battery can using the Ni-plated steel sheet.
  • Ni-plated steel sheet has been popularly used for manufacturing a battery can.
  • Ni is diffused in the steel sheet by heat treatment.
  • patent document 1 JP-A-61-235594 discloses a Ni-plated steel sheet where Ni plating is applied to a steel sheet at an adhesion amount of 9 to 62g/m 2 for one-side surface before diffusion by heating and, thereafter, heat treatment is applied to the steel sheet thus forming an Fe-Ni alloy layer having a thickness of 4 ⁇ m or less on the steel sheet, and a method of manufacturing such a Ni-plated steel sheet.
  • patent document 2 Japanese Patent 3045612 discloses an Ni-plated steel sheet used for manufacturing a battery can where a Ni-plating layer is formed on a cold-rolled steel sheet and, thereafter, thermal diffusion treatment is applied to the steel sheet thus turning the Ni-plating layer into an Fe-Ni diffusion layer.
  • Patent document 3 relates to a specific battery can, a specific sheet for forming the battery can, and a specific method for manufacturing the sheet.
  • Patent document 4 discloses a specific iron-nickel alloy sheet and a specific production method thereof.
  • Patent document 5 discloses a Ni-plated steel sheet for manufacturing a battery can, having a Fe-Ni diffusion layer as an outermost surface layer, said outermost surface layer showing a surface roughness Ra of 0.1 to 1 ⁇ m and a surface roughness Ry of 1 to 10 ⁇ m.
  • the Ni-plated steel sheets disclosed in the above-mentioned patent documents 1 and 2 have the Fe-Ni diffusion layer which is obtained by diffusion by heating on an outermost surface layer and hence, scratches are generated on an outer surface of a battery can in a press operation where a press fluid used as a lubricant in a drawing step is formed of a water-soluble emulsion-based fluid thus giving rise to a drawback in terms of quality.
  • Scratches are flaws which are generated on an outer surface wall of a can after forming the can and flaws which are generated linearly in the pressing direction. As the reason scratches are generated, it is considered that a substance which becomes a factor for generating flaws on a can wall adheres to a die of a mold. Particularly, in case of a Ni-plated steel sheet having a Fe-Ni diffusion layer, when the Ni-plated steel sheet is brought into contact with the mold, minute Ni powder adheres to the mold. It is thought that when a press operation is repeated several hundred thousand times, most of Ni is peeled off and falls. However, some Ni does not fall thus giving rise to a phenomenon where Ni adheres to Ni so that Ni gradually grows.
  • Ni adheres to the die of the mold, Ni is not peeled off even when the press operation is repeated thus giving rise to a phenomenon referred to as build-up where the adhered Ni gradually grows.
  • Ni which adheres to the mold and is built up on the mold in a stage where an adhered Ni grows to a certain size, generates flaws on a wall of a worked product (can) at the time of forming the product thus generating scratches on the wall.
  • the Ni-plated steel sheet of the present invention can prevent Ni from adhering to a mold and from being built up at the time of forming a battery can thus preventing the generation of scratches on the battery can.
  • a low carbon aluminum-killed hot-rolled coil is used as an original sheet of a Ni-plated steel sheet.
  • a coil which is formed of extremely-low carbon steel which contains 0.003 weight% or less of carbon or a coil which is formed of non-aging continuous cast steel manufactured by adding niobium and titanium to the extremely-low carbon steel.
  • a scale (oxide film) formed on a surface of a cold-rolled steel sheet is removed by applying electrolytic cleaning or cleaning by immersion to the cold-rolled sheet using an alkali solution containing caustic soda as a main agent. After the scale is removed, the steel sheet is rolled to a product thickness in a cold-rolling step.
  • the steel sheet After rolling oil which adheres to the steel sheet in rolling is cleaned by electrolytic cleaning, the steel sheet is annealed.
  • Annealing may be performed by either one of continuous annealing and box annealing, and is not limited specifically.
  • Ni plating is applied to the steel sheet.
  • Ni sulfate bath which is referred to as a watt bath is mainly used as a Ni plating bath
  • a sulfamate plating bath besides the Ni sulfamate plating bath, a sulfamic acid bath, a fluoroborate plating bath, a chloride bath or the like can be used.
  • a coating amount of Ni plating in performing plating using these bathes is not specifically limited. However, to set an exposure ratio of Fe in a surface layer to a value which falls within a range from 20 to 50% in thermal diffusion treatment which is performed after plating, the coating amount of Ni is preferably set to 0.3 to 2.0 ⁇ m.
  • the plating thickness can be acquired under the electrolysis conditions where in a bath having the bath composition containing 200 to 350g/l of Ni sulfate, 20 to 50g/l of Ni chloride and 20 to 50g/l of boric acid, pH is set to 3.6 to 4.6 and a bath temperature is set to 50 to 65°C, current density is set to 5 to 50A/dm 2 and the number of coulomb is set to approximately 300 to 1500c/dm 2 .
  • Ni plating where organic compounds are not added to a plating bath except for a pit suppressing agent dull plating where an organic compound referred to as leveling agent which makes a precipitated crystal surface of a plating layer smooth is added to a plating bath, and bright Ni plating where an organic compound which contains sulfur component for making a plating layer glossy by making the Ni plating crystal structure fine by further adding a leveling agent is added to a plating bath are named.
  • Ni plating where an organic compound containing a sulfur component is added to a bath is not preferably adopted as Ni plating according to the present invention.
  • heat treatment for forming a Fe-Ni diffusion layer is performed after Ni plating.
  • This heat treatment is provided for increasing adhesiveness between base steel and a plating layer by softening and recrystallizing an extremely fine crystal state of Ni plating as it is, and also for controlling an exposure ratio of Fe in an uppermost surface layer of the Fe-Ni diffusion layer formed by heat treatment.
  • a method for diffusing Ni by heat treatment a method which uses a continuous annealing furnace or a method which uses a box-like annealing furnace is named.
  • a Ni diffusion temperature falls within a range from 600°C to 800°C
  • Ni diffusion time falls within a range from 60 seconds to 12 hours.
  • the Ni diffusion treatment may be performed for more than 12 hours.
  • a gas atmosphere may be a non-oxidization gas atmosphere or a reduction protective gas atmosphere.
  • a heat treatment method by box annealing preferably used is heat treatment which uses a protective gas consisting of 75% of hydrogen and 25% of nitrogen produced by an ammonia crack method referred to as hydrogen rich annealing with favorable heat transfer.
  • a protective gas consisting of 75% of hydrogen and 25% of nitrogen produced by an ammonia crack method referred to as hydrogen rich annealing with favorable heat transfer.
  • the method has an advantageous effect that the irregularities of the Fe-Ni diffusion layer in the inside of the steel strip or the irregularities of the Fe-Ni diffusion layer between steel strips can be made small.
  • Heat treatment conditions are variously changed corresponding to respective plating thicknesses, and a thickness of a Fe-Ni diffusion layer is obtained by a method where the thickness is calculated based on a result obtained by a glow discharge atomic emission spectrochemical analysis (GDS analysis), while an Fe/(Fe+Ni) ratio is obtained by Auger electron spectroscopy.
  • GDS analysis glow discharge atomic emission spectrochemical analysis
  • GDS analysis is a measuring method which acquires an analysis chart in the depth direction, and is a method where it is considered that an element exists when a peak intensity ratio between Fe and Ni falls within a range from a highest peak value to a value which is 1/10 of the highest peak value. Accordingly, even when Fe diffuses in a surface layer, so long as the intensity ratio between Fe and Ni is 1/10 of the highest value or below, the surface layer is recognized as a free Ni layer.
  • a thickness of the Fe-Ni diffusion layer is obtained by calculation by comparing a GDS result of a sample to which plating is applied with the thermal diffusion treatment with a GDS result of a sample to which plating is applied without thermal diffusion treatment.
  • the exposure ratio of Fe which does not generate scratches caused by build-up falls with in a range from 20 to 50%, and more preferably within a range from 30 to 40%.
  • the exposure ratio of Fe is less than 20%
  • the ratio of Ni in the outermost surface layer is increased so that Ni built up on a mold, and the build-up Ni generates scratches on an outer surface of a can.
  • the steel sheet After diffusion treatment, the steel sheet is rolled by temper rolling so that mechanical properties are imparted to the steel sheet, and the surface roughness of the Fe-Ni diffusion layer is adjusted to a predetermined roughness.
  • the surface roughness Ra of the Fe-Ni diffusion layer is set to a value which falls within a range from 0.9 to 2.0 ⁇ m. The generation of scratches is not observed in the steel sheets having the surface roughness Ra of 0.9 to 2.0 ⁇ m.
  • the surface roughness Ra exceeds 2 . 0 ⁇ m, since irregularities on the surface of the Fe-Ni diffusion layer becomes large, an iron base material which forms a substrate below the Fe-Ni alloy layer is liable to be exposed. Accordingly, the surface roughness Ra exceeding 2.0 ⁇ m is detrimental from a viewpoint of ensuring the corrosion resistance of the steel sheet.
  • the surface roughness Ra exceeding 2.0 ⁇ m is detrimental also from a viewpoint of manufacturing the Ni-plated steel sheet.
  • the surface roughness Ry also exhibits the tendency similar to the tendency of the surface roughness Ra.
  • the surface roughness Ry is set to a value which falls within a range of 4.0 to 15 ⁇ m.
  • the reason why an upper limit and a lower limit of the range of the surface roughness Ry is decided is as same as the reason set forth in conjunction with the surface roughness Ra.
  • the surface roughness Ry exceeds 15 ⁇ m, since irregularities on the surface of Fe-Ni diffusion layer becomes large, an iron base material which forms a substrate below the Fe-Ni alloy layer is liable to be exposed. Accordingly, the surface roughness Ry exceeding 15 ⁇ m is detrimental from a viewpoint of ensuring the corrosion resistance of the steel sheet.
  • Ra is an arithmetic average height of a roughness curve and an average value of absolute value deviations from an average line
  • Ry is a maximum height and indicates a height from the lowermost bottom part to the uppermost top part for every reference length.
  • Measuring methods of Ra, Ry are not specifically limited provided that a roughness meter adopting a traceable surface roughness measuring method is used.
  • a measurement device is based on the description of JIS-B0651-2001.
  • the measurement is performed as follows in the present invention.
  • One example of measuring method is described as follows .
  • a traceable surface roughness measurement device (surf com series) made by TOKYO SEMITSU CO. , LTD. is used. JIS' 94 is adopted as the measuring condition. That is, the measurement is performed under the conditions where an evaluation length: 5mm, a measuring speed: 0.4mm/sec, a cut-off value: 1.0mm, a kind of a filter: Gaussian, a measuring range: ⁇ 50 ⁇ m, gradient correction: straight, and a cut-off ratio: 400.
  • the surface roughnesses Ra, Ry depend on rolling roughness and a rolling load in a temper rolling step.
  • Rolls used for temper rolling are not specifically limited, and EDT rolls can also be used besides shot dull rolls. That is, the rolls for temper rolling are not specifically limited provided that a method where the roughness falls within a range called for in Claims is adopted. Further, a temper rolling facility is not also specifically limited.
  • a battery can is formed using a Ni-plated steel sheet manufactured by a manufacturing method of the present invention.
  • a method of forming a battery can is forming by drawing. Usually, water-soluble emulsion is used as a press lubrication material.
  • a Ni-plated steel sheet is formed into a cup in a first step and, thereafter, the cup is formed so as to have a diameter of a battery can through drawing in three to six stages in total, and the cup is formed into a battery can through further four stages.
  • the battery can is formed such that a thickness of a can wall is gradually increased in the direction toward an opening part of the battery can on which a negative pole cap is mounted from a bottom (positive pole terminal part) of the battery can.
  • the can is molded such that the thickness of the can wall in each step is gradually increased toward the opening part from the bottom of the can.
  • sintered hard alloy is preferably used as a material of the mold used for such press forming.
  • the material of the mold is not specifically limited. In the present invention, materials described in Table 1 can be used.
  • an alloy which particularly is apt to generate scratches on the battery can is an alloy which contains Ni as a binder.
  • Ni in the steel sheet surface layer and Ni in the mold alloy cause sticking thus increasing a possibility that a build-up of Ni is formed.
  • Ni binder sintered hard alloys are indicated by WC-Ni (see Table 1).
  • Table 1 kind of material composition densit y hardne ss resista nce force compressi ve strength Young's modulus thermal conductiv ity g/m 2 HrA GPa GPa GPa W/m ⁇ K G3 WC-Co 14.7 89.5 2.6 4.7 579 71 NR8 WC-Ni 14.8 90 2.3 4.2 600 75 NR11 WC-Ni 13.5 90 2.4 4.6 530 63 NM15 WC-Ni 14 86.5 2.5 3.5 530 50 RCCL WC-TiC-TaC 14.7 93 1 3.6 640 70 TM2 Ti-TiC-Mo 5.2 54 0.7 - 250 9.2 TW3 Ti-TiC-Mo-W 5.5-5 .8 68 0.5 - 226 9.2 DUX40 TiC-Ni 6.5 91.5 1.8 3.9 470 29 SiC SiC 3.2 94
  • hot water can be used for cleaning after forming a can so that it is unnecessary to use an organic solvent whereby cleaning can be easily performed while taking into account the environment.
  • Liquid having the above-mentioned composition is mixed, and is further diluted with water thus producing water-soluble emulsion having the concentration of 2 to 10%.
  • Fig. 1 is a cross-sectional constitutional view of a Ni-plated steel sheet of the example where scratches are not generated
  • Fig. 2 is a cross-sectional constitutional view of a Ni-plated steel sheet of a comparison example where scratches are generated.
  • a low carbon aluminum-killed steel sheet having a sheet thickness of 0.25mm and after being treated by cold-rolling and annealing is used as an original sheet.
  • composition of a steel sheet which constitutes the original sheet is as follows.
  • the steel sheet is subjected to alkali electrolytic cleaning and pickling by immersion into a sulfuric acid and, thereafter, Ni plating is applied to the steel sheet under a condition of watt bath matte plating.
  • a Ni plating adhesion amount is set to 0.3 ⁇ m. After Ni performing Ni plating, the steel sheet is subjected to water cleaning and drying. Then, the steel sheet is subjected to heat treatment in a gas atmosphere furnace with an HNX gas (dew point: -20°C) containing 6.5% of hydrogen at a heating temperature of 580°C for a soaking period of 6 hours and, subsequently, the steel sheet is subjected to temper rolling with elongation of 1.2%.
  • HNX gas dew point: -20°C
  • a thickness of the obtained Fe-Ni diffusion layer is 0.5 ⁇ m.
  • Ni-plated steel sheets are obtained in the same manner as the example 1 except for that a Ni plating adhesion amount is changed to values shown in Table 2.
  • a heat treatment temperature and a heat treatment time are changed in a gas atmosphere furnace, and heat treatment condition is controlled such that thicknesses and iron exposure ratios of various Fe-Ni diffusion layers are obtained.
  • an amount of free Ni, a thickness of Fe-Ni diffusion layer, a Fe exposure ratio (%) and surface roughnesses (Ra, Ry) of the obtained Ni-plated steel sheet are shown in Table 2.
  • a battery can for AA size alkali battery is formed by drawing the Ni-plated steel sheets described in examples 1 to 15 using the above-mentioned water-soluble emulsion.
  • the forming is performed through 10 steps, wherein the Ni-plated steel sheet is subjected to drawing and ironing such that a cup has an outer diameter of a battery can through 1 to 6 steps, and the cup is subjected to shoulder forming, final shoulder forming, step forming and cutting of ears through 7 to 8 steps thus forming a battery can.
  • a press operation is performed by transfer drawing and ironing.
  • a material of apart of a mold which is brought into contact with the steel sheet is made of a WC-Ni material (NR-8) which uses a Ni binder.
  • An AA size battery can is formed after shoulder forming, final shoulder forming, step forming and cutting of ears.
  • An outer surface of the battery is observed after the sixth step at which drawing is finished, and the generation of scratches is checked.
  • a thickness of a Fe-Ni diffusion layer is obtained by a GDS analysis, and a Fe/Fe+Ni ratio of an outermost surface layer, that is, an amount of Fe present in an outermost surface layer is measured by an Auger analysis.
  • Ni-plated steel sheets of comparison examples 1 to 6 are prepared, and AA size battery cans are formed in the same manner as the examples.
  • Ni-plated steel sheets of the examples 1 to 15 which fall within the scope of the present invention exhibit no generation of scratches as can be clearly understood from Table 2 and hence, these Ni-plated steel sheet are used as excellent Ni-plated steel sheet for forming battery cans.
  • the Ni-plated steel sheets of the comparison examples 1 to 6 which do not fall within the scope of the present invention exhibit the generation of scratches and hence, these Ni-plated steel sheets do not have practicability.
  • the Fe-Ni diffusion layer may be formed on an outermost surface layer, and surface roughness and a ratio of Fe may be set to the above-mentioned values.
  • another layer may be provided between the Fe-Ni diffusion layer and the steel sheet.
  • a Ni-plated steel sheet where the generation of scratches at the time of forming a battery can is suppressed and a method of manufacturing a battery can which uses such a Ni-plated steel sheet are provided and hence, the present invention possesses an extremely high industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Metal Rolling (AREA)
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Claims (4)

  1. Ein Ni-plattiertes Stahlblech mit einer Fe-Ni-Diffusionsschicht als eine äußerste Oberflächenschicht, wobei
    eine Oberflächenrauigkeit Ra 0,9 bis 2,0 µm beträgt,
    eine Oberflächenrauigkeit Ry 4,0 bis 15 µm beträgt, und
    ein Expositionsverhältnis zwischen Fe und Ni in der Fe-Ni-Diffusionsschicht so eingestellt ist, dass Fe in einer Auger-Analyse 20 bis 50% ausmacht.
  2. Das Ni-plattierte Stahlblech nach Anspruch 1, wobei das Ni-plattierte Stahlblech ein Ni-plattiertes Stahlblech zur Herstellung eines Batteriegehäuses ist, das durch Ziehen unter Verwendung einer Flüssigkeit, die eine wasserlösliche Emulsion als Pressflüssigkeit enthält, gebildet wird.
  3. Ein Verfahren zur Herstellung eines Ni-plattierten Stahlblechs, umfassend die Schritte:
    Aufbringen einer Ni-Plattierung auf eine Oberfläche eines Stahlblechs mit einer Ni-Beschichtungsmenge von 0,3 bis 2 µm;
    Bilden einer Fe-Ni-Diffusionsschicht als eine äußerste Oberflächenschicht des Ni-plattierten Stahlblechs durch Erwärmen des Ni-plattierten Stahlblechs bei einer Temperatur von 600 bis 800°C, so dass ein Expositionsverhältnis zwischen Fe und Ni in der Fe-Ni-Diffusionsschicht so eingestellt ist, dass Fe in einer Auger-Analyse 20 bis 50% ausmacht; und
    Temperwalzen des Stahlblechs, und somit Einstellen einer Oberflächenrauhigkeit Ra der Fe-Ni-Diffusionsschicht auf 0,9 bis 2,0 µm und einer Oberflächenrauhigkeit Ry der Fe-Ni-Diffusionsschicht auf 4,0 bis 15 µm.
  4. Ein Verfahren zur Herstellung eines Batteriegehäuses, wobei ein Ni-plattiertes Stahlblech, welches eine Fe-Ni-Diffusionsschicht als eine äußerste Oberflächenschicht aufweist und wobei die Fe-Ni-Diffusionsschicht eine Oberflächenrauhigkeit Ra von 0,9 bis 2,0 µm und eine Oberflächenrauhigkeit Ry von 4,0 bis 15 µm aufweist und die Fe-Ni-Diffusionsschicht eine derartige Fe/Ni-Expositionsrate aufweist, dass Fe in einer Auger-Analyse 20 bis 50 % ausmacht, Ziehen unter Verwendung einer wasserlöslichen Flüssigkeit, die eine wasserlösliche Emulsion als Pressschmiermittel enthält, unterzogen wird.
EP10785906.8A 2009-06-09 2010-05-31 Nickelplattiertes stahlblech und verfahren zur herstellung eines batteriegehäuses unter verwendung des nickelplattierten stahlblechs Active EP2441532B1 (de)

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US20120171518A1 (en) 2012-07-05
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EP2441532A4 (de) 2017-02-01
US8734961B2 (en) 2014-05-27
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